CN101688052A - Aqueous dispersion of conductive polymer comprising inorganic nanoparticles - Google Patents

Abstract

This invention relates to conductive polymer compositions and their application in electronic devices. The compositions comprise an aqueous dispersion of at least one conductive polymer incorporated with at least one highly fluorinated acid polymer, and inorganic nanoparticles.

Description

Aqueous dispersion of conductive polymer comprising inorganic nanoparticles

Background of the invention

field of invention

The present invention generally relates to conductive polymer compositions comprising inorganic nanoparticles and their use in electronic devices.

Background technique

Electronic devices define a class of products that include an active layer. Organic electronic devices have at least one organic active layer. Such devices may convert electrical energy to radiation (eg, light emitting diodes), detect signals electronically, convert radiation into electrical energy (eg, photovoltaic cells), or include one or more organic semiconductor layers.

Organic light emitting diodes (OLEDs) are organic electronic devices having organic layers capable of electroluminescence. OLEDs comprising conductive polymers can have the following configurations:

Anode/buffer layer/EL material/cathode

and have additional layers between the electrodes. The anode is typically any material capable of injecting holes into the EL material, such as indium tin oxide (ITO). The anode can optionally be supported on a glass or plastic substrate. EL materials include fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. The cathode is generally any material (eg Ca or Ba) capable of injecting electrons into the EL material. Conductive polymers with low electrical conductivity in the range of 10 ⁻³ to 10 ⁻⁷ S/cm are generally used as buffer layers in direct contact with conductive inorganic oxide anodes such as ITO.

There is a continuing need for improved cushioning layer materials.

Summary of the invention

The present invention provides a composition comprising an aqueous dispersion of at least one conductive polymer doped with at least one highly fluorinated acid polymer and having inorganic nanoparticles dispersed therein.

In another embodiment, there is provided a film formed from the composition described above.

In another embodiment, electronic devices are provided having at least one layer comprising the above-described thin film.

Brief description of the drawings

The accompanying drawings show the present invention by way of example, but the accompanying drawings do not constitute any limitation to the present invention.

Figure 1 is a schematic diagram of an organic electronic device.

Skilled artisans will appreciate that objects in the drawings are shown for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to provide a better understanding of the embodiments.

Detailed description of the invention

There are many aspects and embodiments described herein which are illustrative only and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more embodiments will be apparent from the following detailed description and claims. The Detailed Description of the Invention first presents definitions and clarifications of terms, then presents conductive polymers, highly fluorinated acid polymers, inorganic nanoparticles, preparation of doped conductive polymer compositions, buffer layers, electronic devices, and finally examples .

1. Definitions and clarifications of terms used in the specification and claims

Before introducing the details of the embodiments described below, some terms are defined or clarified.

The term "conductor" and variations thereof are intended to refer to layer materials, components or structures having electrical properties that enable electrical current to flow through such layer materials, components or structures without a dip in potential. The term is intended to include semiconductors. In some embodiments, the conductor will form a layer having a conductivity of at least 10 ⁻⁷ S/cm.

The term "conductive" when referring to a material is intended to mean a material which is inherently or inherently capable of conducting electricity without the addition of carbon black or conductive metal particles.

The term "polymer" is intended to mean a material having at least one repeating monomer unit. The term includes homopolymers of only one or one type of monomeric unit as well as copolymers of two or more different monomeric units, including copolymers of monomeric units of different species.

The term "acid polymer" refers to a polymer having acidic groups.

The term "acidic group" refers to a group capable of ionizing to donate a hydrogen ion to a Bronsted base.

The term "highly fluorinated" refers to compounds in which at least 90% of the available carbon-bonded hydrogens have been replaced by fluorine.

The terms "fully fluorinated" and "perfluorinated" are used interchangeably and refer to a compound in which all available hydrogens bonded to carbon have been replaced with fluorine.

The composition may comprise one or more different conductive polymers and one or more different highly fluorinated acid polymers.

The term "doped" when referring to a conductive polymer is intended to mean a conductive polymer having polymeric counterions to balance the charge on the conductive polymer.

The term "doped conducting polymer" is intended to mean conducting polymers and polymeric counterions associated therewith.

The term "layer" is used interchangeably with the term "film" and refers to a coating covering a desired area. The term is not limited by size. The area can be as large as an entire device, or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel. Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.

The term "nanoparticle" refers to a material having a particle size of less than 100 nm. In some embodiments, the particle size is less than 10 nm. In some embodiments, the particle size is less than 5 nm.

The term "aqueous" refers to a liquid having a substantial portion of water, and in one embodiment at least about 40% by weight water; in some embodiments, at least about 60% by weight water.

The term "hole transport" when referring to a layer, material, member or structure is intended to mean that such layer, material, member or structure facilitates the passage of positive charges through said layer with relatively high efficiency and with little charge loss, The thickness of a material, member or structure is migrated.

The term "electron transport" when referring to a layer, material, member or structure means that such layer, material, member or structure facilitates or facilitates the migration of negative charges through said layer, material, member or structure to another layer, material , component or structure.

The term "organic electronic device" is intended to mean a device comprising one or more semiconducting layers or materials. Organic electronic devices include, but are not limited to: (1) devices that convert electrical energy into radiation (such as light-emitting diodes, light-emitting diode displays, diode lasers, or light-emitting panels); (2) devices that detect signals electronically (such as photodetectors , photoconductors, photoresistors, photoswitches, phototransistors, photocells, infrared ("IR") detectors, or biosensors); (3) devices that convert radiation into electrical energy (such as photovoltaic devices or solar cells) and (4) a device (such as a transistor or a diode) comprising one or more electronic components which in turn comprise one or more organic semiconductor layers.

As used herein, the terms "comprises," "including," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to the process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, "or" means an inclusive "or", not an exclusive "or". For example, the condition "A or B" is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is is real (or exists), and both A and B are real (or exist).

Likewise, use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table use the "New Nomenclature" convention as described in "CRC Handbook of Chemistry and Physics", 81, (2000-2001).

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the chemical formulae, the letters Q, R, T, W, X, Y and Z are used to designate the atoms or groups defined therein. All other letters are used to refer to conventional atomic symbols. Group numbers corresponding to columns within the Periodic Table of the Elements use the "new nomenclature" convention as described in "CRC Handbook of Chemistry and Physics", 81, (2000).

Many details about specific materials, processing methods, and circuits not described herein are conventional and can be found in textbooks and other sources in the fields of OLED displays, light sources, photodetectors, photovoltaics, and semiconductor components.

2. Conductive polymer

Any conductive polymer can be used in the novel compositions. In some embodiments, the conductive polymer will form a film with a conductivity greater than 10 ⁻⁷ S/cm.

Conductive polymers suitable for the novel composition are made from at least one monomer which, when polymerized alone, forms a conductive homopolymer. Such monomers are referred to herein as "conductive precursor monomers". Monomers that form nonconductive homopolymers when polymerized alone are referred to as "nonconductive precursor monomers." The conductive polymer can be a homopolymer or a copolymer. Conductive copolymers suitable for use in the novel compositions can be made from two or more conductive precursor monomers, or from a combination of one or more conductive precursor monomers and one or more non-conductive precursor monomers .

In some embodiments, the conductive polymer is made from at least one conductive precursor monomer selected from thiophene, pyrrole, aniline, and polycyclic aromatic compounds. The term "polycyclic aromatic compound" refers to a compound having more than one aromatic ring. The rings may be joined by one or more bonds, or they may be fused together. The term "aromatic ring" is intended to include heteroaromatic rings. A "polycyclic heteroaromatic" compound has at least one heteroaromatic ring.

In some embodiments, the conductive polymer is made from at least one precursor monomer selected from the group consisting of thiophene, selenophene, tellurophene, pyrrole, aniline, and polycyclic aromatic compounds. Polymers made from these monomers are referred to herein as polythiophenes, poly(selenophenes), poly(tellophenes), polypyrroles, polyanilines, and polycyclic aromatic polymers, respectively. The term "polycyclic aromatic compound" refers to a compound having more than one aromatic ring. The rings may be joined by one or more bonds, or they may be fused together. The term "aromatic ring" is intended to include heteroaromatic rings. A "polycyclic heteroaromatic" compound has at least one heteroaromatic ring. In some embodiments, the polycyclic aromatic polymer is polythienothiophene.

In some embodiments, monomers contemplated for use in forming the conductive polymers in the novel compositions include Formula I below:

in:

Q is selected from S, Se and Te;

R ^are independently selected such that they are the same or different at each occurrence and are selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl , aralkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, Arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate (ester), ether, ether carboxylate (ester), amidosulfonate (ester), ethersulfonate (ester), estersulfonate (ester), and urethane; or two ^R groups together may form an alkylene or alkenylene chain , thereby obtaining a 3, 4, 5, 6, or 7-membered aromatic or aliphatic ring, which may optionally contain one or more divalent nitrogen, selenium, tellurium, sulfur, or oxygen atoms.

As used herein, the term "alkyl" refers to a group derived from an aliphatic hydrocarbon, which includes unsubstituted or substituted straight chain, branched chain and cyclic groups. The term "heteroalkyl" is intended to mean an alkyl group in which one or more carbon atoms of the alkyl group are replaced by another atom (eg, nitrogen, oxygen, sulfur, etc.). The term "alkylene" refers to an alkyl group having two points of attachment.

As used herein, the term "alkenyl" refers to a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, and includes straight chain, branched chain and cyclic groups which may be unsubstituted or substituted. The term "heteroalkenyl" is intended to mean an alkenyl group in which one or more carbon atoms of the alkenyl group are replaced by another atom (eg, nitrogen, oxygen, sulfur, etc.). The term "alkenylene" refers to an alkenyl group having two points of attachment.

As used herein, the following terms for substituents refer to the chemical formula given below:

"Alcohol" -R ³ -OH

"Amido" -R ³ -C(O)N(R ⁶ )R ⁶

"Amidosulfonate" -R ³ -C(O)N(R ⁶ )R ⁴ -SO ₃ Z

"Benzyl" -CH ₂ -C ₆ H ₅

"Carboxylate (ester)" -R ³ -C(O)OZ or -R ³ -OC(O)-Z

"Ether" -R ³ -(OR ⁵ ) _p -OR ⁵

"Ether carboxylate (ester)" -R ³ -OR ⁴ -C(O)OZ or -R ³ -OR ⁴ -OC(O)-Z

"Ether sulfonate (ester)" -R ³ -OR ⁴ -SO ₃ Z

"Ester sulfonate (ester)" -R ³ -OC(O)-R ⁴ -SO ₃ Z

"Sulfonimide" -R ³ -SO ₂ -NH-SO ₂ -R ⁵

"Urethane" -R ³ -OC(O)-N(R ⁶ ) ₂

wherein all "R" groups are the same or different at each occurrence, and:

R ³ is a single bond or an alkylene group

R ⁴ is alkylene

R ⁵ is alkyl

^R6 is hydrogen or alkyl

p is 0 or an integer from 1 to 20

Z is H, alkali metal, alkaline earth metal, N(R ⁵ ) ₄ or R ⁵

Any of the above groups may also be unsubstituted or substituted, and any group may have F in place of one or more hydrogens, including perfluorinated groups. In some embodiments, the alkyl and alkylene groups have 1 to 20 carbon atoms.

In some embodiments, two R ¹ in the monomer together form -W-(CY ¹ Y ² ) _m -W-, wherein m is 2 or 3, W is O, S, Se, PO, NR ⁶ , Y ¹ is the same or different at each occurrence and is hydrogen or fluorine, Y ² is the same or different at each occurrence and is selected from hydrogen, halogen, alkyl, alcohol, amidosulfonate (ester), benzyl, carboxylate (ester), ether, ether carboxylate (ester), ether sulfonate (ester), ester sulfonate (ester), and urethane, where the Y group can be partially or fully fluorinated. In some embodiments, all Y are hydrogen. In some embodiments, the polymer is poly(3,4-ethylenedioxythiophene). In some embodiments, at least one Y group is not hydrogen. In some embodiments, at least one Y group is a substituent having F, wherein the F replaces at least one hydrogen. In some embodiments, at least one Y group is perfluorinated.

In some embodiments, the monomer has Formula I(a):

in:

Q is selected from S, Se and Te;

^R is the same or different at each occurrence, and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, Ether, ether carboxylate (ester), ether sulfonate (ester), ester sulfonate (ester) and urethane, with the proviso that at least one ^R is not hydrogen, and

m is 2 or 3.

In some embodiments of Formula I(a), m is 2, one R ⁷ is alkyl of more than 5 carbon atoms, and all other R ⁷ are hydrogen.

In some embodiments of Formula I(a), at least one ^R group is fluorinated. In some embodiments, at least one ^R group has at least one fluorine substituent. In some embodiments, the ^R group is fully fluorinated.

In some embodiments of formula I(a), the ^R7 substituent on the fused alicyclic ring of the monomer can provide improved aqueous solubility of the monomer and facilitate polymerization in the presence of the fluorinated acid polymer.

In some embodiments of Formula I(a), m is 2, one R ⁷ is sulfonic acid-propylene-ether-methylene, and all other R ⁷ are hydrogen. In some embodiments, m is 2, one R ⁷ is propyl-ether-ethylene, and all other R ⁷ are hydrogen. In some embodiments, m is 2, one R ⁷ is methoxy, and all other R ⁷ are hydrogen. In some embodiments, one R ⁷ is difluoromethylene sulfonate methylene (—CH ₂ —OC(O)—CF ₂ —SO ₃ H), and all other R ⁷ are hydrogen.

In some embodiments, the pyrrole monomers contemplated for use in forming the conductive polymers in the novel compositions comprise Formula II below.

Wherein in formula II:

^{R is} independently selected such that it is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl radical, aralkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl , arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate (ester), ether, amidosulfonate salt (ester), ether carboxylate (ester), ether sulfonate (ester), ester sulfonate (ester), and urethane; or two ^R groups together can form an alkylene or alkenylene chain, thereby obtaining 3, 4, 5, 6, or 7 membered aromatic rings or alicyclic rings, which rings may optionally contain one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms; and

^R is independently selected such that it is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, Epoxides, silanes, siloxanes, alcohols, benzyls, carboxylates, ethers, ether carboxylates, ether sulfonates, ester sulfonates and urethanes .

In some embodiments, ^R is the same or different at each occurrence and is independently selected from hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate ( ester), ether, amido sulfonate (ester), ether carboxylate (ester), ether sulfonate (ester), ester sulfonate (ester), urethane, epoxy, silane, siloxane , and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, or siloxane moieties.

In some embodiments, R ^is selected from hydrogen, alkyl, and sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane, or siloxane moieties. One or more substituted alkyl groups.

In some embodiments, the pyrrole monomer is ^{unsubstituted} and R and ^R are both hydrogen.

In some embodiments, two ^R together form a 6- or 7-membered alicyclic ring further selected from the group consisting of alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate ( Ester), ether sulfonate (ester), ester sulfonate (ester) and urethane group substitution. These groups improve the solubility of the monomer and the resulting polymer. In some embodiments, two R ¹ are taken together to form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group. In some embodiments, two R ¹ together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group having at least 1 carbon atom.

In some embodiments, two R ^'s are taken together to form -O-(CHY) _m -O-, where m is 2 or 3 and Y is the same or different at each occurrence and is selected from hydrogen, alkyl, alcohol, benzyl , carboxylate (ester), amidosulfonate (ester), ether, ether carboxylate (ester), ether sulfonate (ester), ester sulfonate (ester) and urethane. In some embodiments, at least one Y group is not hydrogen. In some embodiments, at least one Y group is a substituent having F, wherein the F replaces at least one hydrogen. In some embodiments, at least one Y group is perfluorinated.

In some embodiments, aniline monomers contemplated for use in forming the conductive polymers in the novel compositions include Formula III below.

in:

a is 0 or an integer from 1 to 4;

b is an integer from 1 to 5, provided that a+b=5; and

^R independently selected such that the same or different at each occurrence is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl , aralkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, Arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate (ester), ether, ether carboxylate (ester), amidosulfonate (ester), ethersulfonate (ester), estersulfonate (ester), and urethane; or two ^R groups together may form an alkylene or alkenylene chain , thereby obtaining a 3, 4, 5, 6, or 7 membered aromatic or aliphatic ring, which may optionally contain one or more divalent nitrogen, sulfur, or oxygen atoms.

When polymerized, the aniline monomeric unit may have formula IV(a) or formula IV(b), as shown below, or a combination of the two formulas.

wherein a, b and ^R1 are as defined above.

In some embodiments, the aniline monomer is unsubstituted and a=0.

In some embodiments, a is not 0 and at least one R ¹ is fluorinated. In some embodiments, at least one R ¹ is perfluorinated.

In some embodiments, the fused polycyclic heteroaromatic monomers contemplated for use in forming the conductive polymers in the novel compositions have two or more fused aromatic rings, at least one of which is a heteroaromatic ring. In some embodiments, the fused polycyclic heteroaromatic monomer has the formula V:

in:

Q is S, Se, Te, or NR ⁶ ;

R ⁶ is hydrogen or alkyl;

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independently selected such that they are the same or different at each occurrence and are selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, Alkylthioalkyl, alkylaryl, aralkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, Arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxyl acid salts, ethers, ether carboxylates, amido sulfonates, ether sulfonates, ester sulfonates and urethanes; and

At least one pair of R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹¹ together form an alkenylene chain, resulting in a 5- or 6-membered aromatic ring, which may optionally contain one or more Divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms.

In some embodiments, the fused polycyclic heteroaromatic monomer has a formula selected from the group consisting of V(a), V(b), V(c), V(d), V(e), V(f), V(g), V(h), V(i), V(j) and V(k):

in:

Q is S, Se, Te, or NH; and

T is the same or different at each occurrence and is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te and PR ⁶ ;

Y is N; and

R ⁶ is hydrogen or alkyl.

The fused polycyclic heteroaromatic monomer can be further selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate , ester sulfonate (ester) and urethane group substitution. In some embodiments, the substituents are fluorinated. In some embodiments, the substituents are fully fluorinated.

In some embodiments, the fused polycyclic heteroaromatic monomer is thienothiophene. Such compounds have been discussed eg in Macromolecules, 34, 5746-5747 (2001) and Macromolecules, 35, 7281-7286 (2002). In some embodiments, the thienothiophene is selected from thieno(2,3-b)thiophene, thieno(3,2-b)thiophene, and thieno(3,4-b)thiophene. In some embodiments, the thienothiophene monomer is further selected from the group consisting of alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate ), ester sulfonate (ester) and at least one group substitution of urethane. In some embodiments, the substituents are fluorinated. In some embodiments, the substituents are fully fluorinated.

In some embodiments, polycyclic heteroaromatic monomers contemplated for use in forming polymers in the novel compositions include Formula VI:

in:

Q is S, Se, Te, or NR ⁶ ;

T is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te and PR ⁶ ;

E is selected from alkenylene, arylene and heteroarylene;

R ⁶ is hydrogen or alkyl;

R ¹² is the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, aralkyl , amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl , acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate (ester), ether, ether carboxylate (ester) ), amidosulfonate (ester), ethersulfonate (ester), estersulfonate (ester) and urethane; or two ^R groups together can form an alkylene or alkenylene chain, thereby A 3, 4, 5, 6, or 7 membered aromatic or aliphatic ring is obtained, which ring may optionally contain one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms.

In some embodiments, the conductive polymer is a copolymer of a precursor monomer and at least one second monomer. Any type of second monomer can be used as long as it does not adversely affect the desired properties of the copolymer. In some embodiments, the second monomer makes up no more than 50% of the polymer based on the total number of monomer units. In some embodiments, the second monomer is no more than 30% of the polymer based on the total number of monomer units. In some embodiments, the second monomer is no more than 10% of the polymer based on the total number of monomer units.

Exemplary types of second monomers include, but are not limited to, alkenyl, alkynyl, arylene, and heteroarylene. Examples of the second monomer include, but are not limited to, fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylene vinylene, phenylene acetylene, pyridine, diazine, and triazine, all of which can be further substituted.

In some embodiments, the copolymer is prepared by first forming an intermediate precursor monomer having the structure A-B-C, where A and C represent precursor monomers, which may be the same or different, and B represents a second monomer. A-B-C intermediate precursor monomers can be prepared using standard organic synthesis techniques such as Yamamoto, Stille, Grignard metathesis, Suzuki and Negishi coupling reactions. A copolymer is then formed by oxidative polymerization of this intermediate precursor monomer alone, or with one or more other precursor monomers.

In some embodiments, the conductive polymer is selected from polythiophenes, polypyrroles, fused polycyclic heteroaromatic polymers, copolymers thereof, and combinations thereof.

In some embodiments, the conductive polymer is selected from poly(3,4-ethylenedioxythiophene), unsubstituted polypyrrole, poly(thieno(2,3-b)thiophene), poly(thieno(3 , 2-b)thiophene), and poly(thieno(3,4-b)thiophene).

3. Highly Fluorinated Acid Polymers

A highly fluorinated acid polymer ("HFAP") can be any polymer that is highly fluorinated and has acidic groups bearing acidic protons. The acidic groups donate ionizable protons. In some embodiments, the acidic proton has a pKa value of less than 3. In some embodiments, the acidic proton has a pKa value less than zero. In some embodiments, the acidic proton has a pKa value of less than -5. The acid group can be attached directly to the polymer backbone, or it can be attached to a side chain of the polymer backbone. Examples of acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The acid groups may all be the same, or the polymer may have more than one type of acid group. In some embodiments, the acidic group is selected from sulfonic acid groups, sulfonamide groups, and combinations thereof.

In some embodiments, the HFAP is at least 95% fluorinated; in some embodiments, it is fully fluorinated.

In some embodiments, the HFAP is water soluble. In some embodiments, the HFAP is dispersible in water. In some embodiments, the HFAP is organic solvent wettable. The term "organic solvent wettable" means that the contact angle formed by the material with an organic solvent when forming a thin film is not greater than 60°C. In some embodiments, the wettable material forms a film that is wettable by phenylhexane with a contact angle of no greater than 55°. Methods of measuring contact angles are well known. In some embodiments, wettable materials can be made from polymeric acids that are not inherently wettable but can be made wettable with selected additives.

Examples of suitable polymer backbones include, but are not limited to: polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, aramids, polyacrylamides, polystyrene, and copolymers thereof compounds, all of which are highly fluorinated; in some embodiments fully fluorinated.

In one embodiment, the acidic group is a sulfonic acid group or a sulfonimide group. A sulfonimide group has the formula:

-SO ₂ -NH-SO ₂ -R

wherein R is an alkyl group.

In one embodiment, the acidic group is located on the fluorinated side chain. In one embodiment, the fluorinated side chains are selected from the group consisting of alkyl, alkoxy, amide, ether, and combinations thereof, all of which are fully fluorinated.

In one embodiment, the HFAP has a highly fluorinated olefin backbone and has highly fluorinated alkyl sulfonates, highly fluorinated ether sulfonates, highly fluorinated ester sulfonates salts (esters), or highly fluorinated ether sulfonimide side groups. In one embodiment, the HFAP is a perfluoroalkene with perfluoro-ether-sulfonic acid side chains. In one embodiment, the polymer is 1,1-difluoroethylene and 2-(1,1-difluoro-2-(trifluoromethyl)allyloxy)-1,1,2,2-tetrafluoroethylene Copolymers of fluoroethanesulfonic acid. In one embodiment, the polymer is ethylene and 2-(2-(1,2,2-trifluoroethyleneoxy)-1,1,2,3,3,3-hexafluoropropoxy)-1 , 1,2,2-copolymers of tetrafluoroethanesulfonic acid. These copolymers can be made into the corresponding sulfonyl fluoride polymers, which can then be converted to the sulfonic acid form.

In one embodiment, the HFAP is a homopolymer or copolymer of fluorinated and partially sulfonated poly(arylene ether sulfone). The copolymer may be a block copolymer.

In one embodiment, HFAP is a sulfonimide polymer having formula IX:

in:

_R is selected from highly fluorinated alkylene, highly fluorinated heteroalkylene, highly fluorinated arylene, and highly fluorinated heteroarylene, which may be substituted by one or more ether oxygen; and

n is at least 4.

In one embodiment of formula IX, _Rf is perfluoroalkyl. In one embodiment, _Rf is perfluorobutyl. In one embodiment, _Rf comprises ether oxygen. In one embodiment, n is greater than 10.

In one embodiment, the HFAP comprises a highly fluorinated polymer backbone and side chains having the formula X:

in:

R ¹⁵ is highly fluorinated alkylene or highly fluorinated heteroalkylene;

R ¹⁶ is highly fluorinated alkyl or highly fluorinated aryl; and

a is 0 or an integer of 1 to 4;

In one embodiment, the HFAP has formula XI:

in:

R ¹⁶ is highly fluorinated alkyl or highly fluorinated aryl;

c is independently 0 or an integer from 1 to 3; and

n is at least 4.

The synthesis of HFAP is described, for example, in A. Feiring et al., "J. Fluorine Chemistry", 2000, 105, 129-135; A. Feiring et al., "Macromolecules", 2000, 33, 9262-9271; D.D. Desmarteau, "J. Fluorine Chem.", 1995, 72, 203-208; A.J. Appleby et al., "J. Electrochem. Soc.", 1993, 140(1), 109-111; and US Patent 5,463,005 to Desmarteau.

In one embodiment, the HFAP further comprises repeat units derived from at least one highly fluorinated ethylenically unsaturated compound. Perfluoroolefins contain 2 to 20 carbon atoms. Representative perfluoroalkenes include, but are not limited to: tetrafluoroethylene, hexafluoropropylene, perfluoro-(2,2-dimethyl-1,3-dioxole), perfluoro-(2-methylene base-4-methyl-1,3-dioxolane), CF ₂ =CFO(CF ₂ ) _t CF=CF ₂ (where t is 1 or 2) and R _f "OCF=CF ₂ (where _Rf " is a saturated perfluoroalkyl group having 1 to about 10 carbon atoms). In one embodiment, the comonomer is tetrafluoroethylene.

In one embodiment, the HFAP is a gel-forming polymeric acid. As used herein, the term "gel-forming" refers to a material that is insoluble in water and forms a colloid when dispersed in an aqueous medium. The gel-forming polymeric acid typically has a molecular weight in the range of about 10,000 to about 4,000,000. In one embodiment, the polymeric acid has a molecular weight of from about 100,000 to about 2,000,000. Colloidal particle sizes typically range from 2 nanometers (nm) to about 140 nm. In one embodiment, the colloid has a particle size of 2 nm to about 30 nm. Highly fluorinated gel-forming polymeric materials with acidic protons can be used. Certain polymers described above can be formed in non-acid form, for example, as salts, esters, or sulfonyl fluorides. They will be converted to the acid form for use in the preparation of the conductive compositions described below.

In some embodiments, the HFAP comprises a highly fluorinated carbon backbone and side chains represented by the formula

-(O-CF ₂ CFR _f ³ ) _a -O-CF ₂ CFR _f ⁴ SO ₃ E ⁵

wherein R _f ³ and R _f ⁴ are independently selected from F, Cl or a highly fluorinated alkyl group having 1 to 10 carbon atoms, a=0, 1 or 2, and E ⁵ . In some cases, ^E5 can be a cation, such as Li, Na, or K, and can be converted to the acid form.

In some embodiments, the HFAP may be a polymer disclosed in US Patent 3,282,875 and US Patents 4,358,545 and 4,940,525. In some embodiments, HFAP comprises a perfluorocarbon backbone with side chains represented by the formula

-O-CF ₂ CF(CF ₃ )-O-CF ₂ CF ₂ SO ₃ E ⁵

wherein ^{E is} as defined above. This type of HFAP is disclosed in US Patent 3,282,875 and can be prepared from tetrafluoroethylene (TFE) and perfluorinated vinyl ether _CF2 =CF-O- _CF2CF ( _CF3 ) _-O - _{CF2CF2SO 2} F. Copolymerization of perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF), followed by conversion of sulfonyl fluoride groups to sulfonate groups by hydrolysis, and in They are prepared by ion exchange where necessary to convert them to the desired ionic form. Examples of polymers ^of this type disclosed in US Pat. _Nos . 4,358,545 and _4,940,525 have side chains -O- _CF2CF2SO3E5 , where ^E5 is as defined above. The polymer can be prepared from tetrafluoroethylene (TFE) and perfluorovinyl ether CF ₂ =CF-O-CF ₂ CF ₂ SO ₂ F, perfluoro(3-oxa-4-pentenesulfonyl fluoride) (POPF) It is prepared by copolymerization followed by hydrolysis and, if necessary, further ion exchange.

分散体的形式从E.I.du Pont deNemours and Company(Wilmington，DE)商购获得。One type of HFAP can contain water

Dispersion forms are commercially available from EI du Pont de Nemours and Company (Wilmington, DE).

4. Inorganic nanoparticles

Inorganic nanoparticles can be insulating or semiconducting.

In some embodiments, the inorganic nanoparticles are metal sulfides or metal oxides. Examples of semiconducting metal oxides include, but are not limited to: mixed valence metal oxides, such as zinc antimonite; and non-stoichiometric metal oxides, such as oxygen-deficient molybdenum trioxide, vanadium pentoxide, and the like. Examples of insulating metal oxides include, but are not limited to, titanium dioxide, zirconia, molybdenum trioxide, vanadium oxide, and aluminum oxide

In some embodiments, the nanoparticles are surface treated with a coupling agent to be compatible with the aqueous conductive polymer. Types of surface modifiers include, but are not limited to, silanes, titanates, zirconates, aluminates, and polymeric dispersants. Surface modifiers contain chemical functional groups, examples of which include, but are not limited to, nitrile, amino, cyano, alkylamino, alkyl, aryl, alkenyl, alkoxy, aryloxy, sulfonic acid, acrylic acid, phosphoric acid, and Alkali metal salts, acrylates (esters), sulfonates (esters), amidosulfonates (esters), ethers, ether sulfonates (esters), ester sulfonates (esters), alkylthio , and arylthio. In one embodiment, chemical functionalities may include linking groups such as epoxy, alkylvinyl, and arylvinyl to react with the conducting polymer in the nanocomposite or hole transport material in the next upper layer . In one embodiment, the surface modifier is fluorinated or perfluorinated, such as tetrafluoro-trifluoroethyl-vinyl-ether-triethoxysilane, perfluorobutane-triethoxysilane , perfluorooctyltriethoxysilane, bis(trifluoropropyl)-tetramethyldisilazane, and bis(3-triethoxysilyl)propyltetrasulfide.

5. Preparation of Doped Conductive Polymer Composition

In the following discussion, conductive polymers, HFAP, and inorganic nanoparticles will be referred to in the singular. However, it should be understood that any more than one or all of these substances may be used.

The preparation method of the novel conductive polymer composition is as follows: first forming a doped conductive polymer, and then adding inorganic nanoparticles.

The doped conductive polymer is formed by oxidative polymerization of precursor monomers in the presence of HFAP in an aqueous medium. Polymerization reactions are described in published US patent applications 2004/0102577, 2004/0127637 and 2005/205860.

Inorganic nanoparticles can be added directly to the doped conductive polymer dispersion in solid form. In some embodiments, the inorganic nanoparticles are dispersed in an aqueous solution, and the dispersion is mixed with the doped conductive polymer dispersion. The weight ratio of nanoparticles to conductive polymer is in the range of 0.1 to 10.0.

In some embodiments, the pH is adjusted up before or after adding the inorganic particles. The dispersion of doped conductive polymer and inorganic nanoparticles can be stable at the pH value thus formed of about 2 to neutral. Adjustment of the pH can be performed using a cation exchange resin prior to the addition of the nanoparticles. In some embodiments, the pH is adjusted by adding an aqueous alkaline solution. The cation of the base may be, but is not limited to, alkali metals, alkaline earth metals, ammonium and alkylammonium. In some embodiments, alkali metals are preferred over alkaline earth metal cations.

Films made from the novel conductive compositions described herein are hereinafter referred to as "the novel films described herein". The films can be prepared using any liquid deposition technique, including continuous and discontinuous techniques. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous spray coating. Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

The films thus formed are smooth and relatively transparent, have a refractive index (at a wavelength of 460 nm) greater than 1.4, and may have electrical conductivity in the range of 10 ⁻⁷ to 10 ⁻³ S/cm.

6. Buffer layer

In another embodiment of the present invention there is provided a buffer layer deposited from an aqueous dispersion comprising the novel conductive polymer composition. The term "buffer layer" or "buffer material" is intended to mean a conductive or semiconductive material, and may serve one or more functions in an organic electronic device, including but not limited to planarization of underlying layers, charge transport and/or Charge injection properties, scavenging of impurities such as oxygen or metal ions, and other aspects that are beneficial or can improve the performance of organic electronic devices. The term "layer" is used interchangeably with the term "film" and refers to a coating covering a desired area. The term is not limited by size. The area can be as large as an entire device, or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel. Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous spray coating. Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

Dry films of the novel conductive polymer compositions are generally not redispersible in water. The buffer layer can thus be applied as several thin layers. Furthermore, the buffer layer can be coated with layers of different water-soluble or water-dispersible materials without damage. Surprisingly, it was found that the buffer layer comprising the novel conductive polymer composition has improved wettability.

In another embodiment, there is provided a buffer layer deposited from an aqueous dispersion containing the novel conductive polymer composition in admixture with other water-soluble or water-dispersible materials. Examples of the types of materials that can be added include, but are not limited to, polymers, dyes, coating aids, organic and inorganic conductive inks and pastes, charge transport materials, crosslinkers, and combinations thereof. Other water soluble or dispersible materials can be simple molecules or polymers. Examples of suitable polymers include, but are not limited to, conductive polymers such as polythiophene, polyaniline, polypyrrole, polyacetylene, poly(thienothiophene), and combinations thereof.

7. Electronic devices

In another embodiment of the present invention there is provided an electronic device comprising at least one electroactive layer positioned between two electrical contact layers, wherein the device further comprises a novel buffer layer. The term "electroactive" when referring to a layer or material is intended to mean a layer or material exhibiting electronic or electroradiative properties. Electroactive layer materials can emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation.

As shown in FIG. 1 , a typical device 100 has an anode layer 110 , a buffer layer 120 , an electroactive layer 130 and a cathode layer 150 . Adjacent to cathode layer 150 is optional electron injection/transport layer 140 .

The device may include a carrier or substrate (not shown), which may be adjacent to the anode layer 110 or the cathode layer 150 . Most commonly, the carrier is adjacent to the anode layer 110 . Supports can be flexible or rigid, organic or inorganic. Examples of carrier materials include, but are not limited to, glass, ceramic, metal, and plastic films.

The anode layer 110 is an electrode more effective for injecting holes than the cathode layer 150 . The anode may comprise materials including metals, mixed metals, alloys, metal oxides or mixed oxides. Suitable materials include mixed oxides of group 2 elements (ie beryllium, magnesium, calcium, strontium, barium, radium), group 11 elements, group 4, 5 and 6 elements, and group 8 to 10 transition elements. If the anode layer 110 is to be light transmissive, mixed oxides of group 12, 13 and 14 elements, such as indium tin oxide, may be used. As used herein, the phrase "mixed oxide" refers to an oxide having two or more different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Some non-limiting specific examples of materials for the anode layer 110 include, but are not limited to, indium tin oxide ("ITO"), indium zinc oxide, aluminum tin oxide, gold, silver, copper, and nickel. Anodes may also comprise organic materials, especially conducting polymers such as polyaniline, including "Flexible light-emitting diodes made from soluble conducting polymer", Nature vol. 357, pp. 477-479 (June 11, 1992) Exemplary materials described in . At least one of the anode and cathode should be at least partially transparent so that the light generated can be observed.

The anode layer 110 may be formed by a chemical or physical vapor deposition method or a spin casting method. Chemical vapor deposition can be performed in the form of plasma enhanced chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("MOCVD"). Physical vapor deposition can include all forms of sputtering (including ion beam sputtering), as well as electron beam evaporation and resistive evaporation forms. Specific forms of physical vapor deposition include radio frequency magnetron sputtering and inductively coupled plasma physical vapor deposition ("IMP-PVD"). These deposition techniques are well known in the art of semiconductor fabrication.

In one embodiment, the anode layer 110 is patterned during a lithographic operation. Patterns can vary as desired. The layer may be patterned by, for example, positioning a patterned mask or resist over the first flexible composite barrier structure prior to application of the first electrical contact layer material. Or alternatively, the layers may be applied as a bulk layer (also known as blanket deposition) which is subsequently patterned using, for example, a patterned resist layer and wet chemical or dry etching techniques. Other patterning methods well known in the art can also be used.

Buffer layer 120 comprises the novel conductive composition described herein. Buffer layers made of conductive polymers doped with HFAP are generally not wettable by organic solvents and have a refractive index below 1.4 (at a wavelength of 460 nm). The buffer layers described herein can be more wettable and thus easier to coat with the next layer from non-polar organic solvents. The buffer layers described herein may also have a refractive index (at 460 nm) greater than 1.4. The buffer layer is typically deposited onto the substrate using a variety of techniques well known to those skilled in the art. As mentioned above, typical deposition techniques include vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.

An optional layer (not shown) may be present between buffer layer 120 and electroactive layer 130 . This layer may contain a hole transport material. Examples of hole transport materials are reviewed, for example, by Y. Wang in "Kirk-Othmer Encyclopedia of Chemical Technology", Fourth Edition, Volume 18, Pages 837 to 860, 1996. Both hole transport molecules and hole transport polymers can be used. Commonly used hole transport molecules include, but are not limited to: 4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4"-tris(N- 3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1' -biphenyl]-4,4'-diamine (TPD); 1,1-bis[(two-4-methylphenylamino)phenyl]cyclohexane (TAPC); N,N'-bis(4 -Methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); Tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA); α-phenyl-4-N,N-diphenyl Aminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis[4-(N,N-diethylamino)-2-methylbenzene base](4-methylphenyl)methane (MPMP); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl] Pyrazoline (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-tetrakis(4-methyl Phenyl)-(1,1'-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthalene-1-yl)-N,N'-bis-(phenyl ) p-diaminobiphenyl (α-NPB); and porphyrin compounds such as copper phthalocyanine. Commonly used hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophene), polyaniline, and polypyrrole. Hole transport polymers can also be obtained by incorporating hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate.

Depending on the application of the device, the electroactive layer 130 can be a light-emitting layer activated by an applied voltage (such as in a light-emitting diode or a light-emitting electrochemical cell), or a material that can respond to radiant energy and generate a signal with or without an applied bias voltage layers (such as in photodetectors). In one embodiment, the electroactive material is an organic electroluminescent ("EL") material. Any EL material can be used in the device, including but not limited to small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Examples of fluorescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal chelated 8-quinolinol compounds, such as tris(8-quinolinolato)aluminum (Alq3); cyclometallic iridium and platinum electroluminescent compounds, such as in Petrov et al. Complexes of iridium and phenylpyridine, phenylquinoline, or phenylpyrimidine ligands disclosed in U.S. Patent 6,670,645 and published PCT patent applications WO 03/063555 and WO 2004/016710, as well as published in, for example, Organometallic complexes described in PCT patent applications WO 03/008424, WO 03/091688, and WO 03/040257, and mixtures thereof. Thompson et al. in US Patent 6,303,238, and Burrows and Thompson in published PCT patent applications WO 00/70655 and WO 01/41512 have described electroluminescent emissive layers comprising charged host materials and metal complexes. Examples of conjugated polymers include, but are not limited to, poly(phenylenevinylene), polyfluorene, poly(spirobifluorene), polythiophene, poly(p-phenylene), copolymers thereof, and mixtures thereof.

Optional layer 140 can serve both to facilitate electron injection/transport and also serve as a confinement layer to prevent quenching reactions at layer interfaces. More specifically, if layer 130 and layer 150 are otherwise in direct contact, layer 140 can facilitate electron mobility and reduce the likelihood of a quenching reaction. Examples of materials for optional layer 140 include, but are not limited to, metal chelating 8-quinolinol compounds such as bis(2-methyl-8-quinolinol)(p-phenyl-phenoxy)aluminum(III)( BAlQ) and tris(8-quinolinolato)aluminum (Alq ₃ ); tetrakis(8-quinolinolato)zirconium; azole compounds such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl Base)-1,3,4-oxadiazole (PBD), 3-(4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-tri Azole (TAZ) and 1,3,5-tris(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline ; phenanthroline derivatives, such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any one or combination of them. Alternatively, optional layer 140 may be inorganic and comprise BaO, LiF, _Li2O , or the like.

The cathode layer 150 is an electrode that is particularly effective for injecting electrons or carrying current carriers. Cathode layer 150 may be any metal or non-metal that has a lower work function than the first electrical contact layer (in this case, anode layer 110). As used herein, the term "lower work function" is intended to mean a material having a work function of no greater than about 4.4 eV. As used herein, "higher work function" is intended to mean a material having a work function of at least about 4.4 eV.

Materials for the cathode layer may be selected from group 1 alkali metals (e.g. lithium, sodium, potassium, rubidium, cesium), group 2 metals (e.g. magnesium, calcium, barium, etc.), group 12 metals, lanthanides (e.g. cerium, samarium, europium, etc.) and actinides (such as thorium, uranium, etc.). Materials such as aluminum, indium, yttrium, and combinations thereof may also be used. Specific non-limiting examples of materials for cathode layer 150 include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof.

Cathode layer 150 is typically formed by chemical or physical vapor deposition methods. In some embodiments, the cathode layer will be patterned as discussed above with respect to the anode layer 110 .

Other layers in the device may be made of any material known to be useful in these layers, depending on the function these layers are intended to provide.

In some embodiments, an encapsulation layer (not shown) is deposited over contact layer 150 to prevent undesirable components such as water and oxygen from entering device 100 . These components may adversely affect the organic layer 130 . In one embodiment, the encapsulation layer is a barrier layer or a film. In one embodiment, the encapsulation layer is a glass cover.

Although not shown, it should be understood that device 100 may include additional layers. Other layers, known or unknown in the art, may be used. Furthermore, any of the above layers may include two or more sublayers, or may form a layered structure. Alternatively, some or all of the anode layer 110, hole transport layer 120, electron transport layer 140, cathode layer 150, and other layers may be treated, especially surface treated, to enhance charge carrier transport efficiency or other physical characteristics of the device. The choice of materials for the various component layers is preferably determined by balancing the goals of providing the device with high device efficiency while considering device lifetime, fabrication time and complexity factors, among other factors understood by those skilled in the art. It should be understood that determining optimal components, component configurations, and compositional characteristics is routine for one of ordinary skill in the art.

，在一个实施方案中为1000至

；缓冲层120，50至

，在一个实施方案中为200至

；光敏层130，10至

，在一个实施方案中为100至

；任选的电子传输层140，50至

，在一个实施方案中为100至

；阴极150，200至

，在一个实施方案中为300至。器件内电子-空穴复合区域的位置可受到每层相对厚度的影响，继而影响器件的发射光谱。因此，选择电子传输层的厚度时，应使得电子-空穴复合区域位于发光层中。所需的各层厚度的比率将取决于所用材料的确切性质。In one embodiment, the different layers have the following thickness ranges: anode 110, 500 to

, in one embodiment from 1000 to

; buffer layer 120, 50 to

, in one embodiment from 200 to

; photosensitive layer 130, 10 to

, in one embodiment from 100 to

; optional electron transport layer 140, 50 to

, in one embodiment from 100 to

; Cathode 150, 200 to

, in one embodiment from 300 to . The location of the electron-hole recombination region within the device can be influenced by the relative thickness of each layer, which in turn affects the emission spectrum of the device. Therefore, the thickness of the electron transport layer should be selected such that the electron-hole recombination region is located in the light emitting layer. The desired ratio of layer thicknesses will depend on the exact nature of the materials used.

In operation, a voltage generated by a suitable power supply (not shown) is applied across device 100 . Current therefore flows through the layers of the device 100 . Electrons enter the organic polymer layer, releasing photons. In certain OLEDs, known as active-matrix OLED displays, each deposit of a light-sensitive organic film can be independently excited by a current path, causing each pixel to emit light. In certain OLEDs, known as passive matrix OLED displays, deposits of photosensitive organic films can be excited by rows and columns of electrical contact layers.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are those described below. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

It is to be understood that, for clarity, those features of the invention which are described above and below with reference to different embodiments may also be presented in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described with reference to a single embodiment, may also be presented separately or in any subcombination. Further, reference to numerical values stated in ranges includes each and every value within that range.

Example

Comparative Example A

This comparative example shows that PAni/ (Low conductivity and non-wettability of poly(tetrafluoroethylene)/perfluoroethersulfonic acid) thin films without the addition of inorganic nanoparticles.

胶态分散体制备。采用与美国专利6,150,426实施例1第2部分相似的方法制备25％(w/w)的

分散体，不同的是温度为约270℃，然后用水将其稀释成12.0％(w/w)的分散体以用于聚合反应。The PAni/ The dispersion adopts water containing water with EW (acid equivalent weight) of 1000

Colloidal Dispersion Preparation. 25% (w/w) of

The dispersion, except that the temperature was about 270°C, was then diluted with water to a 12.0% (w/w) dispersion for polymerization.

分散体(11.57mmol SO₃H基团)和103g水。使用安装有双级螺旋桨叶的顶置式搅拌器，以300RPM的转速搅拌稀释的。向该稀释的

分散体中迅速加入：溶于15mL水的1.21g(5.09mmol)过硫酸钠(Na₂S₂O₈)，以及溶于266微升(9.28mmol)HCl和20mL水的422微升(4.63mmol)苯胺。聚合反应的液体变得不透明并且非常粘稠，但在5分钟内无可见的颜色变化。加入约20mg硫酸铁，但仍无可见变化。然而，聚合反应的液体在30分钟后开始变蓝并在之后变为绿色。大约8小时后，向聚合反应混合物中加入Dowex M31和Dowex M43离子交换树脂各25g，以及100g去离子水。将混合物过夜搅拌，然后用滤纸过滤。向滤液中加入100g去离子水以降低粘度。将滤液分成五等份。In a 500mL reactor, add 96.4g of water containing 12% solids

Dispersion (11.57mmol _SO3H groups) and 103g water. Using an overhead stirrer equipped with two-stage propeller blades, stir the diluted . to the diluted

The dispersion was quickly added: 1.21 g (5.09 mmol) of sodium persulfate (Na ₂ S ₂ O ₈ ) dissolved in 15 mL of water, and 422 µl (4.63 mmol) of 266 µl (9.28 mmol) of HCl and 20 mL of water )aniline. The polymerized liquid became opaque and very viscous, but there was no visible color change within 5 minutes. About 20 mg of ferric sulfate was added, but still no visible change. However, the polymerized liquid started to turn blue after 30 minutes and turned green thereafter. After about 8 hours, 25 grams each of Dowex M31 and Dowex M43 ion exchange resins, and 100 grams of deionized water were added to the polymerization mixture. The mixture was stirred overnight, then filtered through filter paper. 100 g of deionized water was added to the filtrate to reduce the viscosity. The filtrate was divided into five equal portions.

。由该PAni/

制备薄膜，然后在130℃下于空气中烘烤。经测定薄膜的室温导电率为1.2×10^-8S/cm，其也在表1中示出。将一小滴甲苯滴在一片薄膜上，但是甲苯迅速从薄膜上滚落，这表明该薄膜表面不能被非极性有机溶剂润湿。非极性溶剂通常用于发光聚合物以及发光小分子。A part is left as is without adding alkali. The pH value of this part was determined to be 2, and contained 2.88% (w/w) of PAni/

. by the PAni/

Films were prepared and then baked at 130°C in air. The room temperature conductivity of the film was measured to be 1.2×10 ⁻⁸ S/cm, which is also shown in Table 1. A small drop of toluene was dropped on a piece of film, but the toluene rolled off the film quickly, which indicated that the surface of the film was not wettable by non-polar organic solvents. Nonpolar solvents are commonly used for light-emitting polymers as well as light-emitting small molecules.

中加入0.1M NaOH水溶液，将pH值调至5.0。经测定，该部分含Na⁺分散体包含2.89％(w/w)的PAni/

。由pH值为5.0的PAni/

制成的薄膜的导电率经测定为3.8×10^-8S/cm，其也在表1中示出。经测试，该PAni/

薄膜不能被甲苯润湿。To the second part of PAni/ with a pH value of 2

0.1M NaOH aqueous solution was added to adjust the pH value to 5.0. It was determined that this portion of the Na ⁺ -containing dispersion contained 2.89% (w/w) of PAni/

. From PAni/ with a pH value of 5.0

The electrical conductivity of the produced thin film was determined to be 3.8×10 ⁻⁸ S/cm, which is also shown in Table 1. After testing, the PAni/

The film cannot be wetted by toluene.

Example 1

(聚(四氟乙烯)/全氟醚磺酸)薄膜的导电率和可润湿性方面的影响。This example shows the role of semiconductor nanoparticles in enhancing PAni/

(Poly(tetrafluoroethylene)/perfluoroether sulfonic acid) film conductivity and wettability.

分散体用于说明本发明的实施方案。向5.0166g pH值为2的PAni/

分散体中加入1.1313g Celnax CX-Z300H-

(一种含水亚锑酸锌分散体，得自NissanChemical Industries，Ltd.Houston，Texas，USA)。CX-Z300H-F2具有为约7的pH值，并含有26.47％(w/w)的亚锑酸锌颗粒，其粒度小于20nm。配方中PAni/

聚合物与亚锑酸锌的重量比率为约0.47。混合物形成了稳定的分散体，历经至少五个月也无颗粒沉淀的迹象。在烘干水分后，其还形成了光滑、透明的薄膜。数据清楚地表明Celnax CX-Z300H-

中的特定亚锑酸锡颗粒与PAni/

相容。然而，为了改善表面光滑度，使粗糙度低于至少5nm，该方法需要通过更耗能的方法加以改善，而不是简单地将两种组分加在一起。经测定，含有PAni/

和亚锑酸锌的分散体在室温下的薄膜导电率为6.6×10^{- 4}S/cm(两个薄膜样本的平均值)，其也在表1中示出。导电率被提高了四个数量级以上。让一片薄膜与一滴甲苯接触。甲苯容易地在薄膜表面蔓延，这表明该薄膜可被常用的非极性有机溶剂润湿。The pH value prepared in Comparative Example 1 is 2 and the PAni/pH value of 5.0

Dispersions are used to illustrate embodiments of the invention. To 5.0166g PAni/ with a pH value of 2

To the dispersion was added 1.1313g Celnax CX-Z300H-

(an aqueous zinc antimonite dispersion available from Nissan Chemical Industries, Ltd. Houston, Texas, USA). CX-Z300H-F2 has a pH of about 7 and contains 26.47% (w/w) zinc antimonite particles with a particle size of less than 20 nm. PAni/

The weight ratio of polymer to zinc antimonite was about 0.47. The mixture formed a stable dispersion with no evidence of particle settling for at least five months. It also forms a smooth, clear film after drying off the moisture. The data clearly show that the Celnax CX-Z300H-

Specific tin antimonite particles in PAni/

compatible. However, to improve surface smoothness to a roughness below at least 5nm, this approach needs to be improved by more energy-intensive methods than simply adding the two components together. After determination, containing PAni/

The film conductivity of the dispersion with zinc antimonite at room temperature is 6.6× ^{10 −4 S} /cm (average value of two film samples), which is also shown in Table 1. The conductivity is improved by more than four orders of magnitude. Expose a piece of film to a drop of toluene. Toluene spread easily on the surface of the film, which indicated that the film was wettable by commonly used non-polar organic solvents.

中加入CX-Z300H-F2，以确定其对导电率和可润湿性的影响。向5.0666g pH值为5.0的PAni/

分散体中加入1.1450g Celnax CX-Z300H-

。配方中PAni/

聚合物与亚锑酸锌的重量比率为约0.47。混合物形成了稳定的分散体，并无颗粒沉淀的迹象。在烘干水分后，它还形成了光滑、透明的薄膜。数据清楚地表明Celnax CX-Z300H-

中的特定亚锑酸锡颗粒与PAni/

相容。然而，为了改善表面光滑度，使粗糙度低于至少5nm，该方法需要通过更耗能的方法来加以改善，而不是简单地将两种组分加在一起。经测定，含PAni/和亚锑酸锌的分散体在室温下的薄膜导电率为9.3×10^-4S/cm(两个薄膜样本的平均值)，其也在表1中示出。导电率被提高了四个数量级以上。让一片薄膜与一滴甲苯接触。甲苯容易地在薄膜表面延展，这表明薄膜可被常用的非极性有机溶剂润湿。Also to PAni/ at pH 5.0

CX-Z300H-F2 was added to determine its effect on conductivity and wettability. To 5.0666g PAni/ with a pH value of 5.0

Add 1.1450g Celnax CX-Z300H-

. PAni/

The weight ratio of polymer to zinc antimonite was about 0.47. The mixture formed a stable dispersion with no evidence of particle settling. It also forms a smooth, clear film after drying off the moisture. The data clearly show that the Celnax CX-Z300H-

Specific tin antimonite particles in PAni/

compatible. However, to improve surface smoothness down to a roughness below at least 5nm, this approach needs to be improved by a more energy-intensive approach than simply adding the two components together. After determination, containing PAni/ and zinc antimonite dispersion at room temperature had a film conductivity of 9.3×10 ⁻⁴ S/cm (average of two film samples), which is also shown in Table 1. The conductivity is improved by more than four orders of magnitude. Expose a piece of film to a drop of toluene. Toluene spreads easily on the surface of the film, which indicates that the film is wettable by commonly used non-polar organic solvents.

Table 1

Effect of CX-Z300H-F2 on conductivity

It should be noted that not all of the acts described above in the general description or in the examples are required, that some of the specific acts are not required, and that one or more of the acts may be implemented in addition to those described other behavior. Furthermore, the order in which the acts are listed is not necessarily the order in which they are performed.

In the foregoing specification, concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art recognizes that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, the specification and drawings are to be regarded as illustrative rather than restrictive, and all such modifications are intended to be included within the scope of the present invention.

Benefits, other advantages, and solutions to problems have been described above in conjunction with specific embodiments. However, benefits, advantages, solutions to problems, and any feature that may cause any benefit, advantage or solution to be produced or made more pronounced, are not to be construed as critical, required or essential features of any or all claims.

It will be appreciated that, for clarity, certain features that are described herein in the context of different implementations can also be provided in combination in a single implementation. Conversely, various features which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

The use of numerical values in the various ranges stated herein are stated as approximations, as if the word "about" preceded the minimum and maximum values in the stated ranges. Thus, slight variations in values above and below the stated ranges can be used to obtain substantially the same results as values within these ranges. Moreover, the disclosure of these ranges is also intended to be a continuous range including each value between the minimum and maximum average values, which includes the resulting range when certain components of one value are mixed with those of different values. partial value. However, when wider and narrower ranges are disclosed, it is also within the contemplation of the invention that the minimum value from one range be matched with the maximum value from the other range, and vice versa.

Claims (15)

1. composition, described composition comprises:

Be mixed with the aqueous dispersion of at least a conductive polymers of at least a highly fluorinated acid polymer, and

Inorganic nanoparticles, wherein said nano particle is semiconductive or insulating.

2. the composition of claim 1, wherein said conductive polymers are selected from Polythiophene, poly-(selenophen), poly-(tellurium fen), polypyrrole, polyaniline, polycyclic aromatic polymkeric substance, their multipolymer and their combination.

3. the composition of claim 2, wherein said conductive polymers is selected from unsubstituted polyaniline, poly-(3,4-enedioxy thiophene), unsubstituted polypyrrole, poly-(thieno-(2,3-b) thiophene), poly-(thieno-(3,2-b) thiophene) and poly-(thieno-(3,4-b) thiophene).

4. the composition of claim 1, the degree of fluorination of wherein said highly fluorinated acid polymer is at least 95%.

5. the composition of claim 1, wherein said highly fluorinated acid polymer is selected from sulfonic acid and sulfimide.

6. the composition of claim 1, wherein said highly fluorinated acid polymer is the perfluoroolefine with perfluor-ether-sulfonic acid side chain.

7. the composition of claim 1, wherein said highly fluorinated acid polymer is selected from vinylidene fluoride and 2-(1,1-two fluoro-2-(trifluoromethyl) allyloxys)-1,1,2, the multipolymer of 2-tetrafluoro ethyl sulfonic acid and ethene and 2-(2-(1,2,2-trifluoro-ethylene oxygen base)-1,1,2,3,3,3-hexafluoro propoxy-)-1,1,2, the multipolymer of 2-tetrafluoro ethyl sulfonic acid.

8. the composition of claim 1, wherein said highly fluorinated acid polymer is selected from the multipolymer of tetrafluoroethylene and perfluor (3,6-two oxa-s-4-methyl-7-octene sulfonic acid), and the multipolymer of tetrafluoroethylene and perfluor (3-oxa--4-amylene sulfonic acid).

9. the composition of claim 1, wherein said nano particle is selected from metallic sulfide, metal oxide and their combination.

10. the composition of claim 9, wherein said metal oxide is selected from antimonous acid zinc, anoxybiotic molybdic oxide, vanadium pentoxide and their combination.

11. the composition of claim 1, wherein said nano particle are selected from titanium dioxide, zirconium white, molybdic oxide, vanadium oxide, aluminum oxide and their combination.

12. the composition of claim 1, wherein the weight ratio of nano particle and conductive polymers is in 0.1 to 10.0 scope.

13. the film of making by the described composition of claim 1.

14. the film of claim 13, described film have the refractive index greater than 1.4 under 460nm.

15. electron device, described electron device comprise at least one layer of being made by the composition of claim 1.

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